Cotton-dyestuffs.



' No Drawing.

To all whom it mag, concern Be it known that" we, AUGUST BLANK, CARL Hninnnnnicir, and JOIIANNES JANsnN, doctors of philosophy, chemists, citizens of the German Empire, residing at Leverkusen, near Cologne-on-the-RhinE, Germany, have 'invented new and useful Improvements in,

Cott'omDyestuffs, of which the following. is a specification. v

\Ve have found that new and valuable cotton dyestuffs can be obtained b combining. the tetrazo compounds of diammodiphenylureas:

'NH-C5H4-NHCONHCaH4-NH2 with one molecule of a sulfonic acid which can be further diazotized after copulation, rediazotizing and coupling with two molecules of the same or two different azo dyestuff components, such as resorcin, metaphenylenediamin, meta-aminophenol, etc. These dyestuffs of the present invention have the following graphically represented constitution: v R-n=-N-cm-NH co-nn-ctui-n=n-n' n:N-R=

in which R and R are end. components and R the radical of an aromatic sulfonic acid. The new products are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water generally with a brownish coloration. They dye cotton brown shades. These colors are rendered very fast to washing by aftcrtreatment with formaldehyde of fibers dyed with them. a

In order to illustrate the new process more fully the following example is given, the

parts being by weight :12.1 parts of metadiaminodiphenylurea are dissolved in 150 parts of hot water and parts of hydrochloric acid, the solution is cooled with ice to 0 C. and is tctrazoized with a solution of 6.9 parts of sodium nitrite. Subsequently to the tetrazo compound a solution of 12 parts of 2- lIHlIlO-8-llnPlltliOl-GSlllfOIllC acid in 250 parts of water and 25 parts of soda is added. The production of! intermediate compound is soon complete. The mass of the reaction is then acidulated with,50 parts of hydrochloric acid and a solution of parts of nitrite is added. After'a 3-5 hours stirring, to the tetrazo compound a solution of 18 parts of ineta-phenylenediamin hydro- Speeification of Letters Patent.

chlorid in-water is added and the liquid is.

UNITED STATES T QFFICE.

AUGUST BLANK, CARL HEIDENREICH, AND JOHA'NNES JANSE lfl', OF LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNORS TO FARBENFABRIK E'N VORM. FRIEDR. BAYER & (30., OF ELBER-FELD, GERMANY, A CORPORATION OF GERM;\NY.

COTTON-DYESTUFFS.

Patented Dec. 30, 1913-.

Application filed April 29, 1913. Serial No. 764,354.

rendered distinctly alkaline. The azo dye is salted out. It is after being dried and pulverized in the shape of its sodium salt a dark powder soluble in water with a brown coloration and being soluble in concentrated sulfuric acid of 66 Be. with a brown coloration. It has in a free state most probably the formula:

Upon treatment with stannous chlorid and hydrochloric acid the dye is decomposed, carbonic, metaphenylenediamin, triaminobenzene, Q.7diamino-8-naphthol-G-sulfonic acid being obtained.-- It. dyes cotton in brightbrown shades, which are rendered fast to ashing by an aftertreatment with formaldehyde. Dyes of quite similar properties are obtained from para-para-diaminodiphcnylurea. Other intermediate compounds can be used, such as 1.6- or 1.7- naphthylamin snlfonic acid (or a mixture thereof), 2.5.7-an'linonaphthol .sulfonic acid, metzi-phtmylencdiamin sulfonic acid or other end components, such as meta-toluylenediamiii,"resorcin, aminophenol, etc. Of course two different end components can be used.

lVe claim 1. The herein described new cotton dyestuffs being trisazo-dyestuffs containing a diphenylurea group, which dyes are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water generally with a brownish coloration and dyeing cotton in brown shades, which are rendered very fast to washing by an aftertreatment with formaldehyde of fibers dyed with them, substantially as described.

2. The hereindescribed new cotton dyestuffs of the following general formula:

in which'R and R are suitable end components and R the radical of an aromatic sulfonic acid, which dyes are after being dried and pulverized in the shape of their alkaline salts, dark powders soluble in water generallywith a brownish coloration and dyeing cotton in brown shades, which are rendered very fast to washing by an after-treatmentwith formaldehyde of fibers dyed with them, substantially as described.

3.,The herein described new cotton dyestuffs of the following .general formula:

where R and R are end components containing amino groups and R the radicalof an aromatic sulfonic acid, which dyes are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water generally with a brownish coloration and dyeing cotton in brown shades, which are rendered ver fast to washin b an after treatment with formaldehyde of fibers dyed with them, substantially as described.

5. The'hereln described new cotton dye; stuffs of the following general formula:

R-N=NCGH4-NHCOCJLN=N-R=N-R2 where R and R are end components containing amino groups and R the radical of a naphthalene sulfonic acid, which dyes are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water generally with a brownish coloration and dyeing cotton in brown shades, which arerendered very fast to washing by an after treatment with formaldehyde of fibers dyed with them, substantially as described.

6. The herein described new cotton dye-.

stuif having in a free state most probably the formula:

which is after being dried and pulverized in the shape of its sodium salt a dark powder soluble in water with a brown coloration and being soluble in concentrated sulfuric acid of 66 B. with a brown coloration; yielding upon reduction with stannous chlorid and hydrochloric acid carbonic acid, metaphenlylenediamin, triarnino-benzene and 2.Zdianiino-S-naphthoh6-sulfonic acid; and dyeing cotton in bright brown shades, which are rendered fast to washing by an aftertreatment with formaldehyde, substantially as described.

.In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

AUGUST BLANK. [L.s.] CARL HEIDENREICH. [L.S.] J OHANNE'S J ANSEN. [12.8.]

lVitnesses HELEN Norm, .ALnnnr NUFER.

Copies of this patent may be obtained for five cents each, by addressing the Commissioner of Patents,

Washington, D. C.

read

I [SEAL] Corrections Late-seem No. 1,082,581.

, 1913, upon the application of August Blank, Carl Heidenreich, and Johannes Jensen,

errors appear in the printed specification requiring correction as follows: Page 1, line 2, for the word tetrazoized, read tetrazotized; same page, line 77, after the word carbonic insertthe word'a'cz'd; page 2, line 12, formula, for

RN.--N. .C,H, .I l oon-N=N-c,H,-nH-coand that the saidLetters Patent should be readwitli these corrections therein that the same may conform to the record ofthe case in the Patent Ofiice.

Signed and sealed this 3rd day of March, A. D., 1914.

J. r. NEWTON,

Actini] 00mmiasi0ner of Patents.

' It is hereby certified that in Letters Patent No. 1,082,581, granted December 30,

of Leverkusen, near Cologne, Germany, for an improvement in Cotton Dyestufls, 

